EP4549512A1 - Kautschukzusammensetzung und gehärtetes produkt daraus - Google Patents

Kautschukzusammensetzung und gehärtetes produkt daraus Download PDF

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Publication number
EP4549512A1
EP4549512A1 EP23830764.9A EP23830764A EP4549512A1 EP 4549512 A1 EP4549512 A1 EP 4549512A1 EP 23830764 A EP23830764 A EP 23830764A EP 4549512 A1 EP4549512 A1 EP 4549512A1
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EP
European Patent Office
Prior art keywords
rubber composition
mass
silica
polyorganosiloxane
acrylic rubber
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP23830764.9A
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English (en)
French (fr)
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EP4549512A4 (de
Inventor
Tatsuya Nakano
Toshiaki Miyauchi
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Denka Co Ltd
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Denka Co Ltd
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Publication date
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Publication of EP4549512A1 publication Critical patent/EP4549512A1/de
Publication of EP4549512A4 publication Critical patent/EP4549512A4/de
Withdrawn legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00Materials not provided for elsewhere
    • C09K3/10Materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K3/1006Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04Homopolymers or copolymers of esters
    • C08L33/06Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062Copolymers with monomers not covered by C08L33/06
    • C08L33/064Copolymers with monomers not covered by C08L33/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16JPISTONS; CYLINDERS; SEALINGS
    • F16J15/00Sealings
    • F16J15/02Sealings between relatively-stationary surfaces
    • F16J15/06Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces
    • F16J15/10Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing
    • F16J15/102Sealings between relatively-stationary surfaces with solid packing compressed between sealing surfaces with non-metallic packing characterised by material
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16JPISTONS; CYLINDERS; SEALINGS
    • F16J15/00Sealings
    • F16J15/16Sealings between relatively-moving surfaces
    • F16J15/32Sealings between relatively-moving surfaces with elastic sealings, e.g. O-rings
    • F16J15/3284Sealings between relatively-moving surfaces with elastic sealings, e.g. O-rings characterised by their structure; Selection of materials
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16LPIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L11/00Hoses, i.e. flexible pipes
    • F16L11/04Hoses, i.e. flexible pipes made of rubber or flexible plastics
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1802C2-(meth)acrylate, e.g. ethyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/22Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
    • C08G77/26Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen nitrogen-containing groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/006Additives being defined by their surface area
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/02Inorganic compounds
    • C09K2200/0243Silica-rich compounds, e.g. silicates, cement, glass
    • C09K2200/0247Silica
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/0615Macromolecular organic compounds, e.g. prepolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09K2200/0625Polyacrylic esters or derivatives thereof
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2200/00Chemical nature of materials in mouldable or extrudable form for sealing or packing joints or covers
    • C09K2200/06Macromolecular organic compounds, e.g. prepolymers
    • C09K2200/068Containing also other elements than carbon, oxygen or nitrogen in the polymer main chain
    • C09K2200/0685Containing silicon

Definitions

  • the present invention relates to a rubber composition and a cured product thereof.
  • a cured product of a rubber composition containing an acrylic rubber is excellent in physical properties such as heat resistance, oil resistance, mechanical properties, and compression set properties, and is widely used as a material such as a hose member, a seal member, or a gasket member in an engine room of automobiles.
  • these automotive members have been required to be more reliable due to the influence of emission control measures, increased engine power, and the like.
  • these members are required to be excellent in strength, elongation and compression set properties.
  • PTL 1 discloses a rubber composition containing a white filler and which can be processed to form a cured product having good mechanical properties.
  • An object of the present invention is to provide a rubber composition which can form a cured product having high strength.
  • the present invention includes the following embodiments.
  • a rubber composition according to the present embodiments includes an acrylic rubber which is a copolymer of monomers containing an alkyl (meth)acrylate, silica, and a polyorganosiloxane having two or more amino groups per molecule.
  • the polyorganosiloxane having two or more amino groups per molecule included in the rubber composition according to the present embodiments is highly compatible with the acrylic rubber, which is the copolymer of monomers containing an alkyl (meth)acrylate, and it is assumed that dispersibility of the silica in the rubber composition is improved.
  • the amino groups of the polyorganosiloxane bond with the acrylic rubber and the siloxane framework is located near the silica, but it is considered that the resulting cured product has improved strength because the silica is highly dispersible. This also allows the cured product to have high elongation.
  • the cured product can also have high compression set properties, which are equivalent to those of conventional rubber compositions using carbon black and rubber compositions using silane coupling agents having amino groups or epoxy groups.
  • the rubber composition according to the present embodiments includes an acrylic rubber, which is a copolymer of monomers containing an alkyl (meth)acrylate.
  • alkyl (meth)acrylate represents an alkyl acrylate and an alkyl methacrylate.
  • alkyl (meth)acrylate examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, n-pentyl (meth)acrylate, isoamyl (meth)acrylate, n-hexyl (meth)acrylate, 2-methylpentyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, n-dodecyl (meth)acrylate, and n-octadecyl (meth)acrylate. These may be used singly or in combination of two or more.
  • alkyl (meth)acrylate an alkyl (meth)acrylate having an alkyl moiety of 1 to 4 carbon atoms is preferable from the viewpoint of the balance of strength/oil resistance/cold resistance.
  • methyl (meta)acrylate, ethyl (meta)acrylate, n-propyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate are preferable.
  • the monomers constituting the copolymer preferably contain 60 to 99% by mass of the alkyl (meth)acrylate, more preferably 70 to 99% by mass, and even more preferably 80 to 98% by mass.
  • the monomers preferably further contain a carboxyl group-containing monomer or an epoxy group-containing monomer.
  • the acrylic rubber according to the present embodiments is preferably a carboxyl group-containing acrylic rubber, which is the copolymer of monomers containing the alkyl (meth)acrylate and the carboxyl group-containing monomer, or an epoxy group-containing acrylic rubber, which is the copolymer of monomers containing the alkyl (meth)acrylate and the epoxy group-containing monomer.
  • the carboxyl group-containing monomer and the epoxy group-containing monomer act as cross-linked seat monomers (monomers having functional groups that form cross-linking points).
  • Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, 2-pentenoic acid, maleic acid, fumaric acid, itaconic acid, a maleic monoalkyl ester, a fumaric monoalkyl ester, mono-cyclohexyl maleate, mono-cyclohexyl fumarate, and cinnamic acid.
  • Examples of the epoxy group-containing monomer include glycidyl acrylate, glycidyl methacrylate, an allyl glycidyl ether, and a methallyl glycidyl ether. These can be used singly or in combination of two or more.
  • the monomers constituting the copolymer contain the carboxyl group-containing monomer or the epoxy group-containing monomer
  • the monomers preferably contain 0.1 to 5% by mass of the carboxyl group-containing monomer or the epoxy group-containing monomer, more preferably 0.5 to 3% by mass, and even more preferably 1 to 2% by mass, from the viewpoint of the balance of strength/elongation.
  • the monomers preferably further contain an olefin in addition to the alkyl (meth)acrylate, and the carboxyl group-containing monomer or the epoxy group-containing monomer.
  • the acrylic rubber according to the present embodiments is preferably the carboxyl group-containing acrylic rubber which is the copolymer of monomers containing the alkyl (meth)acrylate, the carboxyl group-containing monomer, and the olefin, or the epoxy group-containing acrylic rubber which is the copolymer of monomers containing the alkyl (meth)acrylate, the epoxy group-containing monomer, and the olefin.
  • the olefin may improve mechanical properties and cold resistance of the cured product.
  • olefin examples include ethylene, butadiene, and isoprene. These can be used singly or in combination of two or more. Among these, as the olefin, preferable is ethylene, which does not contain double bonds that cause deterioration in heat resistance after reaction.
  • the monomers constituting the copolymer contain the olefin
  • the monomers preferably contain 0.1 to 5% by mass of the olefin, more preferably 0.3 to 4% by mass, and even more preferably 0.5 to 2% by mass, from the viewpoint of the mechanical properties and the like of the cured product.
  • the carboxyl group-containing acrylic rubber which is the copolymer of monomers containing the alkyl (meth)acrylate, the carboxyl group-containing monomer, and the olefin, include DENKA ER A322 (product name, produced by Denka Company Limited), and DENKA ER A413 (product name, produced by Denka Company Limited) as commercially available products.
  • the monomers When the monomers contain the alkyl (meth)acrylate, the epoxy group-containing monomer, and the olefin, the monomers preferably further contain a vinyl carboxylate. That is, the acrylic rubber according to the present embodiments is preferably the epoxy group-containing acrylic rubber which is the copolymer of monomers containing the alkyl (meth)acrylate, the epoxy group-containing monomer, the olefin, and the vinyl carboxylate.
  • the vinyl carboxylate may improve the mechanical properties of the cured product.
  • vinyl carboxylate examples include vinyl acetate, vinyl propionate, vinyl 2-ethylhexanoate, vinyl laurate, and vinyl neodecanoate. These can be used singly or in combination of two or more. Among these, as the vinyl carboxylate, the vinyl acetate is preferable from the viewpoint of the strength.
  • the monomers constituting the copolymer contain the vinyl carboxylate
  • the monomers preferably contain 1 to 20% by mass of the vinyl carboxylate, more preferably 3 to 17% by mass, and even more preferably 5 to 15% by mass, from the viewpoint of the mechanical properties of the cured product.
  • the epoxy group-containing acrylic rubber which is the copolymer of monomers containing the alkyl (meth)acrylate, the epoxy group-containing monomer, the olefin, and the vinyl carboxylate include DENKA ER 5300 (product name, produced by Denka Company Limited) as a commercially available product.
  • the acrylic rubber is obtained by copolymerizing the monomers by using known methods such as emulsion polymerization, suspension polymerization, solution polymerization, and bulk polymerization.
  • the rubber composition according to the present embodiments includes silica as a filler.
  • silica as a filler, the dispersibility of the filler in the rubber composition according to the present embodiments is improved, and the resulting cured product has high strength and elongation.
  • the silica is not limited, but examples include wet silica, dry silica, and silica fume.
  • a BET specific surface area of the silica is preferably 100 to 130 m 2 /g. Since the BET specific surface area of the silica is in the range of 100 to 130 m 2 /g, the agglomeration of silica is prevented, and reinforcement due to the silica is fully expressed. Therefore, the cured product obtained can have high strength.
  • the BET specific surface area is a value measured by a BET method.
  • a mass proportion of the silica to the acrylic rubber is preferably 0.2 to 1.0, more preferably 0.3 to 0.8, and even more preferably 0.4 to 0.6, from the viewpoint of improving the strength and elongation of the cured product.
  • the rubber composition according to the present embodiments includes a polyorganosiloxane having two or more amino groups per molecule.
  • a rubber composition including an acrylic rubber conventionally, when silica has been used as a filler, a silane coupling agent having an amino group or an epoxy group has been used in combination.
  • the polyorganosiloxane having two or more amino groups per molecule is used instead of the silane coupling agent to enable the cured product to have excellent strength.
  • the polyorganosiloxane has high compatibility with the acrylic rubber which is the copolymer of monomers containing the alkyl (meth)acrylate, the dispersibility of the silica is improved and, as a result, the strength of the cured product is assumed to be improved. Also, the cured product has good elongation and compression set properties.
  • the polyorganosiloxane having two or more amino groups per molecule preferably has structural unit (I) as follows, from the viewpoint of improving the strength of the cured product. [R 1 x R a SiO (4-(x+a))/2 ] (I) wherein x is 1, 2, or 3; a is 0, 1, or 2; x+a ⁇ 4; R is each independently methyl, ethyl, propyl, phenyl, or hydroxy; and R 1 is each independently a monovalent organic residue having an NH 2 group.
  • x is preferably 1.
  • a is preferably 1 or 2, and more preferably 1.
  • R is preferably methyl or hydroxy, and more preferably methyl.
  • R 1 include -R 2 -NH 2 , -R 2 -N(R 3 )-NH 2 , and -R 2 -N(R 3 )-R 4 -NH 2 .
  • R 2 and R 4 are each independently alkylene or alkyleneoxy groups having 1 to 20 carbon atoms. It is preferably the alkylene group having 1 to 5 carbon atoms.
  • R 3 is a hydrogen or an alkyl group having 1 to 5 carbon atoms.
  • R 1 is preferably -R 2 -NH 2 .
  • R 2 is an alkylene group having 1 to 5 carbon atoms, preferably an alkylene group having 2 to 4 carbon atoms, and particularly preferably an aminopropyl group.
  • At least two amino groups per molecule of the polyorganosiloxane are preferably located on different R 1 groups, and more preferably located on different structural units (I), and even more preferably located on different structural units I D described later.
  • the polyorganosiloxane according to the present embodiments can further have structural unit (II D ) as follows: [R' 2 SiO 2/2 ] (II D ) wherein R' are identical or different groups (preferably identical groups), and linear, branched, or cyclic organic residues that can be bonded via an oxygen atom.
  • R' are preferably methyl, ethyl, propyl, or phenyl groups, and particularly preferably methyl groups.
  • the polyorganosiloxane according to the present embodiments can further have structural unit (III M ) as follows: [R" 3 SiO 1/2 ] (III M ) wherein R" are identical or different groups, and are hydroxy, linear, branched, or cyclic organic residues that can be bonded via an oxygen atom. R" are preferably hydroxy, methyl, ethyl, propyl, or phenyl groups, and particularly preferably the hydroxy or methyl groups.
  • R" can be identical groups, and be methyl groups.
  • Structural unit (III M ) can also be [(CH 3 ) 2 (HO)SiO 1/2 ].
  • preferable structures of the polyorganosiloxane according to the present embodiments are as follows. [I D ] m [I M ] n [II D ] o [III M ] (2-n) wherein m is in a range of 0 to 40, and n can be 0, 1, or 2. However, m+n is at least 2, and m+n is preferably in a range up to 20. o is in a range of 0 to 1,000. m+o+2 is at least 3.
  • Examples of the polyorganosiloxane having structural unit (I) include STRUKTOL HT750, HT740, and HT760 (product names, produced by Struktol GmbH), KF-864, KF-865, KF-868, and KF-8015 (product names, produced by Shinetsu Silicone Ltd.), DOWSIL BY 16-213 FLUID (product names, produced by Dow Chemical Company), and AMS-132, AMS-152, AMS-162, AMS-163, AMS-191, and AMS-1203 (product names, produced by Gelest Inc.), which have a structure of formula (A) as follows, as commercially available products.
  • a mass proportion of the polyorganosiloxane to the acrylic rubber is preferably 0.005 to 0.08, more preferably 0.007 to 0.07, and even more preferably 0.01 to 0.06, from the viewpoint of improving the strength and elongation of the cured product.
  • a mass proportion of the polyorganosiloxane to the silica is preferably 0.01 to 0.3, more preferably 0.02 to 0.2, and even more preferably 0.02 to 0.1, from the viewpoint of improving the strength and elongation of the cured product.
  • the rubber composition according to the present embodiments may arbitrarily include other components than the acrylic rubber, the silica, and the polyorganosiloxane described above.
  • other components include an antioxidant, a lubricant, a vulcanizing agent, a vulcanization accelerator, a vulcanization retardant, a plasticizer, and a filler.
  • the cured product according to the present embodiments is obtained by curing the rubber composition according to the present embodiments.
  • the cured product is particularly excellent in strength since it is the cured product of the rubber composition according to the present embodiments. Therefore, the cured product can be suitably used for hoses, seals, gaskets, etc.
  • the tensile strength of the cured product was measured in accordance with JIS K6251.
  • the elongation of the cured product was measured in accordance with JIS K6251.
  • the compression set of the cured product was measured at 175°C for 72 hours in accordance with JIS K6262.
  • DENKA ER A322 contains 82 parts by mass of ethyl acrylate, 17 parts by mass of butyl acrylate, 1 part by mass of ethylene, and 2 parts by mass of a carboxyl group-containing monomer, as a polymer composition.
  • the rubber composition was kneaded using a pressure kneader and an open roll mixer, and then a cross-linking reaction was carried out at 170°C for 20 minutes in a press, and then at 170°C for 4 hours in a gear oven. This produced a cured product of the rubber composition.
  • the tensile strength, elongation and compression set of the cured product were measured using the method described above. The results are shown in Table 1.
  • Table 1 the unit for an amount of each component blended is parts by mass, and the blending proportion of each component is given as a mass proportion. The same applies to Tables 2 to 6.
  • Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Acrylic rubber DENKA ER A322 100 100 100 100 100 100 Silica Nipsil ER (BET:100 m 2 /g) 50 - 50 50 Carbon black SRF - 75 - - Polyorganosiloxane STRUKTOL HT750 2 - - - Silane coupling agent Amino group-containing - - 1.1 - Epoxy group-containing - - - 1.5 Silica/Acrylic rubber 0.5 0 0.5 0.5 Polyorganosiloxane/Acrylic rubber 0.02 0 0 0 Polyorganosiloxane/Silica 0.04 - 0 0 0 Tensile strength [MPa] 15.2 11.2 11.6 12.7 Elongation [%] 275 162 131 226 Compression set [%] 24 19 21 29
  • Example 1 using the rubber composition according to the present embodiments, the tensile strength was high compared with conventional Comparative Example 1 using the carbon black as the filler and Comparative Examples 2 and 3 using the amino or epoxy group-containing silane coupling agent. In addition, the elongation was also high, and the compression set was similar.
  • Example 2 Example 1
  • Example 3 Acrylic rubber DENKA ER A322 100 100 100 100 100 Silica Nipsil ER (BET:100 m 2 /g) 50 50 50 50 50 50 Polyorganosiloxane STRUKTOL HT750 1 2 3 4 Silica/Acrylic rubber 0.5 0.5 0.5 0.5 0.5 0.5 Polyorganosiloxane/Acrylic rubber 0.01 0.02 0.03 0.04 Polyorganosiloxane/Silica 0.02 0.04 0.06 0.08 Tensile strength [MPa] 14.4 15.2 15.0 14.7 Elongation [%] 325 275 209 213 Compression set [%] 30 24 20 19
  • the cured products according to the present embodiments showed high tensile strength even when the blended amount of polyorganosiloxane was changed.
  • the elongation and compression set also showed sufficient values for practical use.
  • Example 5 Example 6
  • Example 7 Acrylic rubber DENKA ER A322 100 100 100 Silica Nipsil ER (BET:100 m 2 /g) 40 50 60 Polyorganosiloxane STRUKTOL HT750 2.4 3 3.6 Silica/Acrylic rubber 0.4 0.5 0.6 Polyorganosiloxane/Acrylic rubber 0.024 0.03 0.036 Polyorganosiloxane/Silica 0.06 0.06 0.06 0.06
  • the cured products according to the present embodiments showed high tensile strength even when the blended amount of the silica was changed.
  • the elongation and compression set also showed sufficient values for practical use.
  • Nipsil ER product name, produced by Tosoh Silica Corporation, BET specific surface area: 130 m 2 /g
  • Nipsil ER product name, produced by Tosoh Silica Corporation, BET specific surface area: 100 m 2 /g
  • a rubber composition was prepared in the same manner as in Example 3, to obtain a cured product and evaluated. The results are shown in Table 4.
  • Example 3 Acrylic rubber DENKA ER A322 100 100 Silica Nipsil ER (BET:100 m 2 /g) 50 - Nipsil ER (BET:130 m 2 /g) - 50 Polyorganosiloxane STRUKTOL HT750 3 4 Silica/Acrylic rubber 0.5 0.5 Polyorganosiloxane/Acrylic rubber 0.03 0.04 Polyorganosiloxane/Silica 0.06 0.08 Tensile strength [MPa] 15.0 15.9 Elongation [%] 209 267 Compression set [%] 20 23
  • the cured products according to the present embodiments showed high tensile strength even when the specific surface area of the silica was changed.
  • the elongation and compression set also showed sufficient values for practical use.
  • DENKA ER 5300 contains 44 parts by mass of ethyl acrylate, 36 parts by mass of butyl acrylate, 14 parts by mass of vinyl acetate, 4 parts by mass of ethylene, and 1.6 parts by mass of an epoxy group-containing monomer, as a polymer composition.
  • the acrylic rubber A contains 46 parts by mass of ethyl acrylate, 25 parts by mass of butyl acrylate, 28 parts by mass of butyl methacrylate, 1 part by mass of ethylene, and 1.5 parts by mass of a carboxyl group-containing monomer, as a polymer composition.
  • Example 9 Comparative Example 4
  • Example 10 Comparative Example 5
  • Acrylic rubber DENKA ER 5300 100 100 - - Acrylic rubber A - - 100 100 Silica Nipsil ER (BET:100 m 2 /g) 50 - 50 - Carbon black SRF - 75 - 75
  • Polyorganosiloxane STRUKTOL HT750 3 - 3 - Silica/Acrylic rubber 0.5 0 0.5 0 Polyorganosiloxane/Acrylic rubber 0.03 0 0.03 0 Polyorganosiloxane/Silica 0.06 - 0.06 -
  • Elongation [%] 315 186 244 167 Compression set [%] 60 57 22 19
  • Nipol AR12 contains 50 parts by mass of ethyl acrylate, 50 parts by mass of butyl acrylate, and 1.1 parts by mass of a carboxyl group-containing monomer, as a polymer composition.
  • Hytemp AR212XP contains 65 parts by mass of ethyl acrylate, 34 parts by mass of butyl acrylate, and 0.5 parts by mass of a carboxyl group-containing monomer, as a polymer composition.
  • Racrester CT contains 74 parts by mass of ethyl acrylate, 18 parts by mass of butyl acrylate, 8 parts by mass of butyl methacrylate, and 1.1 parts by mass of a carboxyl group-containing monomer, as a polymer composition.

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  • Engineering & Computer Science (AREA)
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  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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EP23830764.9A 2022-06-30 2023-04-04 Kautschukzusammensetzung und gehärtetes produkt daraus Withdrawn EP4549512A4 (de)

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